EP0267105B1 - Nouvelles oximes éthyléniques dérivés d'esters de l'acide cyclopropane carboxylique, leur procédé et les intermédiaires de préparation et leur application à la lutte contre les parasites - Google Patents

Nouvelles oximes éthyléniques dérivés d'esters de l'acide cyclopropane carboxylique, leur procédé et les intermédiaires de préparation et leur application à la lutte contre les parasites Download PDF

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Publication number
EP0267105B1
EP0267105B1 EP87402440A EP87402440A EP0267105B1 EP 0267105 B1 EP0267105 B1 EP 0267105B1 EP 87402440 A EP87402440 A EP 87402440A EP 87402440 A EP87402440 A EP 87402440A EP 0267105 B1 EP0267105 B1 EP 0267105B1
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EP
European Patent Office
Prior art keywords
radical
carbon atoms
group
formula
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP87402440A
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German (de)
English (en)
French (fr)
Other versions
EP0267105A3 (en
EP0267105A2 (fr
Inventor
Jean Tessier
Jean-Pierre Demoute
Joseph Cadiergue
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sanofi Aventis France
Original Assignee
Roussel Uclaf SA
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Publication date
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Publication of EP0267105A2 publication Critical patent/EP0267105A2/fr
Publication of EP0267105A3 publication Critical patent/EP0267105A3/fr
Application granted granted Critical
Publication of EP0267105B1 publication Critical patent/EP0267105B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C07D213/647—One oxygen atom attached in position 2 or 6 and having in the molecule an acyl radical containing a saturated three-membered ring, e.g. chrysanthemumic acid esters
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A61P33/10—Anthelmintics

Definitions

  • the invention relates to new ethylenic oximes derived from cyclopropanecarboxylic acid esters, their process and the preparation intermediates and their application in the fight against parasites.
  • the compounds of formula I can have a cyclopropanic copula of cis trans structure, cis structure or trans structure.
  • a more particular subject of the invention is the compounds of formula I in which the cyclopropanic copula is of structure 1R, cis or 1R, trans.
  • the subject of the invention is most particularly the products the preparation of which is given later in the experimental part.
  • the subject of the invention is also a process for preparing the compounds of formula I, characterized in that an acid of formula (II) is subjected: its acid chloride or an anhydride of this acid in which A and B retain their previous meaning to the action of an alcohol of formula ROH in which R retains its previous meaning to obtain the corresponding compound of formula (I), and separates if desired, the various stereoisomers possibly obtained.
  • the esterification can be carried out, according to conventional esterification methods, in particular by esterification of the acid with alcohol in the presence of a carbodiimide with or without base.
  • the different stereoisomers can be separated by chromatography.
  • the products of formula (II) are new products and are in themselves one of the objects of the present invention: they can be obtained by reacting, according to the Wittig reaction, a compound of formula (III): A and B retaining their previous meaning and alk representing an alkyl radical containing from 1 to 4 carbon atoms, in the presence of a strong base with an acid of formula (IV) in the open or cyclized form (that is to say in the form of lactone) hemiacetal or a derivative of this acid, to obtain the corresponding compound of formula II.
  • the strong base used is preferably an alkaline alcoholate, for example sodium or potassium terbutylate.
  • the phosphonates used as starting materials are prepared according to the following scheme: A and B retaining their previous meaning.
  • the products of formula I can also be prepared according to methods equivalent to the method described above, this is how the compound of formula (V) can first be prepared: B and R retaining their previous meaning, then reacts this compound of formula (V) with a compound of formula (IV): AONH2 (VI) in which A has the meaning indicated above to obtain the compound of corresponding formula (I).
  • the condensation between the products of formula (V) and a salt of the product of formula (VI) takes place in the presence of a base such as pyridine.
  • the compounds of formula I have interesting properties which allow their use in the fight against parasites. It can be, for example, the fight against plant parasites, local parasites and parasites of warm-blooded animals.
  • the products of formula I in particular have remarkable fly-killing properties.
  • a subject of the invention is therefore the application of the compounds of formula I to the fight against plant parasites and local parasites.
  • the products of formula I can therefore be used in particular for combating insects in the agricultural field, for combating, for example, against aphids, lepidopteran larvae and beetles. They are used in doses of between 10 and 300 g of active ingredient per hectare.
  • the products of formula I can also be used to fight against insects in premises, to fight in particular against flies, mosquitoes and cockroaches.
  • the products of formula I can also be used to combat mites and parasitic nematodes of plants.
  • the compounds of formula I can also be used to fight against parasitic mites of animals, to fight for example against ticks and in particular ticks of the species Boophilus, those of the species Hyalomnia, those of the species Ambliyomnia and those of the species Rhipicephalus or to fight against all kinds of scabies and in particular the sarcoptic scab, the psoroptic scab and the chorioptic scab.
  • a subject of the invention is therefore also compositions intended for combating parasites of warm-blooded animals, parasites of premises and plants, characterized in that they contain at least one of the products of formula I defined below. -above.
  • the invention particularly relates to insecticide compositions containing as active ingredient at least one of the products defined above.
  • compositions are prepared according to the usual methods of the agrochemical industry or of the veterinary industry or of the industry for products intended for animal nutrition.
  • compositions intended for agricultural use and for use in premises may optionally be added with one or more other pesticidal agents.
  • These compositions can be in the form of powders, granules, suspensions, emulsions, solutions, solutions for aerosols, combustible strips, baits or other preparations conventionally used for the use of this kind of compounds.
  • compositions generally contain a vehicle and / or a nonionic surfactant, ensuring moreover a uniform dispersion of the constituent substances of the mixture.
  • vehicle used can be a liquid such as water, alcohol, hydrocarbons or other organic solvents, a mineral, animal or vegetable oil, a powder such as talc, clays, silicates, kiesselguhr or a solid combustible.
  • the insecticidal compositions according to the invention preferably contain from 0.005% to 10% by weight of active material.
  • compositions according to the invention are used in the form of fumigant compositions.
  • compositions according to the invention can then advantageously consist, for the non-active part, of a combustible insecticide coil (or coil), or also of an incombustible fibrous substrate.
  • a heating device such as an electromosquito destroyer.
  • the inert support can be, for example, composed of pyrethrum marc, Tabu powder (or Machilus Thumbergii leaf powder), pyrethrum stem powder, cedar leaf powder , wood powder (such as sawdust), starch and coconut shell powder.
  • the dose of active ingredient can then be, for example, from 0.03 to 1% by weight.
  • the dose of active material can then be, for example, from 0.03 to 95% by weight.
  • compositions according to the invention for use in premises can also be obtained by preparing a sprayable oil based on active principle, this oil soaking the wick of a lamp and then being subjected to combustion.
  • the concentration of the active ingredient incorporated in the oil is preferably from 0.03 to 95% by weight.
  • the insecticidal compositions according to the invention can optionally be added with one or more other pesticidal agents.
  • the acaricide and nematicide compositions can be in particular in the form of powder, granules, suspensions, emulsions, solutions.
  • wettable powders for foliar spraying containing 1 to 80% or liquids for foliar spraying containing 1 to 500 g / l of active ingredient are preferably used. It is also possible to use powders for leaf dusting containing from 0.05 to 3% of active material.
  • liquids are preferably used for soil treatment containing 300 to 500 g / l of active ingredient.
  • the acaricide and nematicide compounds according to the invention are used, preferably in doses of between 1 and 100 g of active material per hectare.
  • the products of the invention are very often incorporated into food compositions in combination with a nutritive mixture suitable for animal feed.
  • the nutritional mixture can vary according to the animal species, it can contain cereals, sugars and grains, soybean, peanut and sunflower meal, meal of animal origin, for example fish meal, synthetic amino acids, mineral salts, vitamins and antioxidants.
  • the invention therefore therefore relates to the food compositions defined above.
  • the compounds of formula I have excellent general tolerance, and the invention therefore also relates to the products of formula I for combating in particular ticks and scabies in humans and animals.
  • the products of the invention can be administered externally, by spraying, by shampooing, by bathing or brushing.
  • the products of the invention for veterinary use can also be administered by brushing the backbone according to the method known as the "pour-on" method, they can also be administered by the digestive or parenteral route.
  • a subject of the invention is also associations endowed with insecticidal, acaricidal or nematicidal activity, characterized in that they contain as active material, on the one hand at least one of the compounds of general formula I, and on the other hand, at least one of the pyrethroid esters chosen from the group consisting of the esters of allethrolones, 3,4,5,6-tetrahydrophthalimido methyl alcohol, 5-benzyl 3-furyl methyl alcohol, 3-phenoxy benzyl alcohols and alpha-cyano 3-phenoxy benzylic alcohols of chrysanthemic acids, by esters of 5-benzyl 3-furyl methyl alcohols of 2,2-dimethyl 3- (2-oxo 3-tetrahydrothiophenylidene methyl) cyclopropane-1- acids carboxylic, by esters of 3-phenoxy benzyl alcohol and alpha-cyano 3-phenoxy benzylic alcohols of 2,2-dimethyl 3- (2,2-dichloro
  • the associations according to the invention present in particular the advantage either of making it possible to combat, by the versatility of their action, a wider range of parasites, or of manifesting, in certain cases, a synergistic effect.
  • Example 1 1R trans 3- [delta Z, 3- (delta Z methoxyimino) 1-butenyl] 2,2-dimethyl cyclopropane carboxylate d'S cyano 1- (3-phenoxyphenyl) methyl, as well as the isomers 3- [delta Z, 3- ( delta E methoxyimino) 1-butenyl], 3- [delta E, 3- (delta E, methoxyimino) 1-butenyl] and 3- [delta E, 3- (delta Z methoxyimino) 1-butenyl].
  • a solution containing 11.4 g of 1R acid, trans 3- [3-methoxyimino 1-butenyll 2,2-dimethyl cyclopropane carboxylic acid (mixture of the 4 E and Z isomers at the double bonds) is cooled to O ⁇ C 11.55 g of S phenocyanol, 120 mg of 4-dimethylaminopyridine and 60 cm3 of methylene chloride. 12.2 g of dicyclohexylcarbodiimide and 60 cm 3 of methylene chloride are introduced at O ⁇ C. Leave to return to room temperature and filtered.
  • Example 2 1R, cis 3- [delta E, 3- (delta E methoxyimino) 1-butenyl] 2,2-dimethyl cyclopropane carboxylate d'S cyano 1- (3-phenoxyphenyl) methyl and the isomers 3- [delta E, 3- (delta Z-methoxyimino) 1-butenyl 3- [delta Z, 3- (delta E-methoxyimino) 1-butenyl, and 3- [delta 2, 3- (delta Z methoxyimino) 1-butenyl].
  • the starting material used namely dimethyl 2-methoxyimino propyl phosphonate, was prepared as follows. 14.5 g of methylhydroxylamine hydrochloride and 40 cm3 of water in a solution containing 22.2 g of dimethyl beta-ketophosphonate are added at 15 ° C. 25 cm3 of pyridine and 235 cm3 of dioxane. The mixture is stirred for one hour at room temperature. It is evaporated to dryness. 250 cm3 of an ice-cold aqueous hydrochloric acid solution and 250 cm3 of methylene chloride are added. Decanted, extracted the aqueous phase with methylene chloride. The organic phases are dried.
  • the test insects are 4-day-old female house flies.
  • the operation is carried out by direct spraying at a concentration of 0.1 g / l in a Kearns and March chamber using as solvent a mixture of acetone (5%) and Isopar L (petroleum solvent) (amount of solvent used 2 ml in a second). 50 insects are used per treatment.
  • the controls are carried out every minute up to 10 minutes, then at 15 minutes and the KT 50 is determined by the usual methods.
  • the tests are carried out by topical application of an acetone solution using the micro manipulator of Arnold on the dorsal thorax of the larvae. 15 larvae are used per dose of product to be tested. The larvae used are larvae of the fourth larval stage, that is to say about 10 days old when they are raised to 24 ⁇ C and 65% relative humidity. After treatment, the individuals are placed on an artificial nutritive medium (Poitout medium).

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • General Health & Medical Sciences (AREA)
  • Food Science & Technology (AREA)
  • Veterinary Medicine (AREA)
  • Environmental Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Animal Husbandry (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Tropical Medicine & Parasitology (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Medicinal Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Furan Compounds (AREA)
  • Pyridine Compounds (AREA)
  • Pyrane Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Indole Compounds (AREA)
EP87402440A 1986-10-30 1987-10-29 Nouvelles oximes éthyléniques dérivés d'esters de l'acide cyclopropane carboxylique, leur procédé et les intermédiaires de préparation et leur application à la lutte contre les parasites Expired - Lifetime EP0267105B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8615124 1986-10-30
FR8615124A FR2606014B1 (fr) 1986-10-30 1986-10-30 Nouvelles oximes ethyleniques derives d'esters de l'acide cyclopropane carboxylique, leur procede de preparation et leur application a la lutte contre les parasites

Publications (3)

Publication Number Publication Date
EP0267105A2 EP0267105A2 (fr) 1988-05-11
EP0267105A3 EP0267105A3 (en) 1988-11-23
EP0267105B1 true EP0267105B1 (fr) 1992-08-12

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ID=9340364

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87402440A Expired - Lifetime EP0267105B1 (fr) 1986-10-30 1987-10-29 Nouvelles oximes éthyléniques dérivés d'esters de l'acide cyclopropane carboxylique, leur procédé et les intermédiaires de préparation et leur application à la lutte contre les parasites

Country Status (5)

Country Link
US (1) US4879302A (ja)
EP (1) EP0267105B1 (ja)
JP (1) JPS63122661A (ja)
DE (1) DE3781092T2 (ja)
FR (1) FR2606014B1 (ja)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5192801A (en) * 1990-02-27 1993-03-09 Roussel Uclaf 3-[2-cyano-2-halo-ethenyl]-2,2-dimethyl-cyclopropanecarboxylates
FR2658819B1 (fr) * 1990-02-27 1993-03-12 Roussel Uclaf Nouveaux esters derives d'acide 3-(2-cyano 2-halogeno ethenyl) 2,2-dimethyl cyclopropanecarboxylique, leur procede de preparation et leur application comme pesticides.
FR2687666A1 (fr) * 1992-02-21 1993-08-27 Roussel Uclaf Nouveaux esters pyrethrinouiques, derives de l'alcool 6-(trifluoromethyl) benzylique, leur procede de preparation et leur application comme pesticides.
FR2708600B1 (fr) * 1993-08-05 1995-09-15 Roussel Uclaf Nouveaux dérivés de l'alcool 6-trifluorométhyl benzylique, leur procédé de préparation et leur application comme pesticides.
EP1065229B1 (en) * 1999-06-30 2004-09-15 Menicon Co., Ltd. Process for preparing a urethane compound for medical instruments
JP3991812B2 (ja) * 2001-12-11 2007-10-17 住友化学株式会社 エステル化合物およびその用途
JP4765353B2 (ja) * 2004-03-22 2011-09-07 住友化学株式会社 （１−アルケニル）シクロプロパン化合物の製造方法
CN101516855B (zh) * 2006-09-15 2011-08-24 住友化学株式会社 环丙烷羧酸酯及其作为杀虫剂的应用

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4622337A (en) * 1972-05-25 1986-11-11 National Research Development Corporation 2,2-dimethyl-3-(2-halovinyl)cyclopropane carboxlic acid ester pesticides
JPS51125739A (en) * 1974-10-01 1976-11-02 Sumitomo Chem Co Ltd Insecticedes and tickicides comprising novel cyclopropane carboxylate esters and their preparation
US4439446A (en) * 1981-12-21 1984-03-27 Shell Oil Company Fluorine-containing oxyiminocyclopropanecarboxylates

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 87, no. 1, 4.juillet 1977, page 108, no. 1139y, Columbus, Ohio, US; & JP-A-76125739 (SUMITOMO CHEMICAL CO. LTD.) 02.11.1976 & CHEMICAL ABSTRACTS TENTH COLLECTIVE INDEX, vol. 86-95, 1977-1981, American Chemical Society, US *

Also Published As

Publication number Publication date
EP0267105A3 (en) 1988-11-23
EP0267105A2 (fr) 1988-05-11
DE3781092D1 (de) 1992-09-17
JPS63122661A (ja) 1988-05-26
DE3781092T2 (de) 1993-03-18
FR2606014A1 (fr) 1988-05-06
FR2606014B1 (fr) 1989-05-05
US4879302A (en) 1989-11-07

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